Herbicidal N-(pyridinylaminocarbonyl)benzenesulfonamides

ABSTRACT

N-(Pyridinylaminocarbonyl)benzenesulfonamides are useful for the regulation of plant growth and as pre-emergence and post-emergence herbicides.

RELATED APPLICATION

This is a division of application Ser. No. 192,034, filed Sept. 29,1980, now U.S. Pat. No. 4,293,330, which is a continuation-in-part of mycopending application U.S. Ser. No. 082,522, filed Oct. 9, 1979, nowabandoned.

BACKGROUND OF THE INVENTION

This invention relates to novelN-(pyridinylaminocarbonyl)benzenesulfonamides. The compounds of thisinvention and their agriculturally suitable salts, are useful asagricultural chemicals, e.g., plant growth regulants and herbicides.

There are a number of references to compounds with the general formula:##STR1## in the literature.

German Pat. No. 1,117,103 (Feb. 11, 1953) discloses ##STR2## as apharmaceutical intermediate.

Logemann, W.; Caprio, W.; and Artini, D.; Farmaco (Pavia), Ed. Sci. 12,589 (1956) discloses the synthesis of ##STR3## which was treated as ahypoglycemic agent.

German Pat. No. 1,012,598 (July 25, 1957) discloses the following asblood sugar lowering and bacteriostatic agents: ##STR4##

R=NH₂ or NO₂ ; ##STR5##

Ruschig, H. et al., Arzneimitt-Foroch, 8, 448 (1958) reports on bloodsugar reducing agents: ##STR6##

R=2-pyridyl; 4-pyridyl; 6-methyl-2-pyridyl; or 2-thiazolyl.

U.S. Pat. No. 2,977,375 (Mar. 28, 1961) and British Pat. No. 797,474(July 2, 1958) disclose the same subject matter as in German Pat. No.1,012,598 mentioned above.

Onishi, S., Yakugaku Zasski 79, 559 (1959) discloses the following,tested as hypoglycemics; ##STR7##

R=2-pyridyl; 3-pyridyl; or 4-pyridyl.

Holland, G. F., J. Org. Chem., 26, 1662 (1961) discloses compounds ofthe following structure tested as antidiabetics. ##STR8##

R=Cl, CH₃. ##STR9##

R₁ =4-picolyl or 6-methyl-2-picolyl.

Brzozowski, Z., Zh. Obsch. Khem., 39, 430 (1969) discloses anilinecomplexes of the following: ##STR10##

R=2-pyridyl or 4-pyridyl.

No use was disclosed.

Brzozowski, Z., Rocz. Chem., 43, 1761 (1961) discloses the synthesis of:##STR11##

R=2-pyridyl; 6-methyl-2-picolyl; or 2-thiazolyl.

German Pat. No. 2,205,194 (Aug. 24, 1972) discloses cardiovascular,hypertensive analgesic and anti-inflammatory drugs, CNS stimulants andantispasmodics. ##STR12## wherein

R₁ =alkylphenylsulfonamido;

R₂ =H or alkyl; and

R=H, carbamoyl, acyl, or arylsulfonyl.

Abon Ouf, A. A., et al., J. Drug. Res., 6, 123 (1974) discloses thefollowing as being related to anti-diabetic drugs. ##STR13##

R=pyridyl.

The presence of undesired vegetation causes substantial damage to usefulcrops, especially agricultural products that satisfy man's basic foodand fiber needs, such as cotton, rice, corn, wheat and the like. Thecurrent population explosion and concomitant world food and fibershortage demand improvements in the efficiency of producing these crops.Preventing or minimizing loss of a portion of such valuable crops bykilling or inhibiting the growth of undesired vegetation is one way ofimproving this efficiency. A wide variety of materials useful forkilling or inhibiting (controlling) the growth of undesirable vegetationis available; such materials are commonly referred to as herbicides. Theneed still exists; however, for more effective herbicides.

SUMMARY OF THE INVENTION

According to this invention, there are provided novel compounds offormula I and their agriculturally suitable salts, e.g., Na, K,alkylammonium, trichloroacetic acid, suitable agricultural compositionscontaining them and methods of using them as general or selectivepre-emergence and post-emergence herbicides and as plant growthregulants: ##STR14## wherein

X is CH₃ --, CH₃ CH₂ -- or CH₃ O;

Y is CH₃ --, CH₃ CH₂ --, CH₃ O--, CH₃ CH₂ O--, Cl, Br or F;

Ar is ##STR15##

R₁ is CO₂ R₄, CF₃, NO₂, Cl, R₅ SO₂ -- or R₆ R₇ NSO₂ --;

R₂ is H, Cl or CH₃ ;

R₃ is Cl;

R₄ is C₁ -C₄ alkyl, C₃ -C₄ alkenyl, ClCH₂ CH₂ -- or CH₃ OCH₂ CH₂ --;

R₅ is C₁ -C₄ alkyl;

R₆ and R₇ are independently CH₃ -- or CH₃ CH₂ --; provided that

when R₂ is Cl or CH₃ --, R₁ must be Cl or NO₂ ;

when R₁ is CF₃, NO₂ or Cl, then X and Y are independently CH₃ -- or CH₃O--.

Preferred independently for their ease of synthesis are those compoundsof Formula I wherein:

(1) R₁ is R₆ R₇ NSO₂ --, R₅ SO₂ --, CO₂ R₄ wherein R₄ is C₁ -C₃ alkyl orallyl, or;

(2) R₁ is NO₂ and R₂ is Cl.

Equally preferred for their ease of synthesis are those compounds ofFormula I wherein:

(3) Y is Cl, Br, CH₃ -- or CH₃ O--.

More preferred are those compounds of preferred (1) wherein:

(4) Y is Cl, Br, CH₃ -- or CH₃ O--.

Specifically preferred for ease of synthesis are the compounds:

2-[[(4,6-dimethyl-2-pyridinyl)aminocarbonyl]aminosulfonyl]benzoic acid,methyl ester;

2-[[(6-methoxy-4-methyl-2-pyridinyl)aminocarbonyl]aminosulfonyl]benzoicacid, methyl ester;

2-[[(6-bromo-4-methyl-2-pyridinyl)aminocarbonyl]aminosulfonyl]benzoicacid, methyl ester; and

N'-[(4,6-dimethyl-2-pyridinyl)aminocarbonyl]-N,N-dimethyl-1,2-benzenedisulfonamide.

Synthesis

As shown in Equation 1, the compounds of formula I can be prepared bycombining an appropriate 2-aminopyridine of formula III with anappropriately substituted sulfonyl isocyanate of formula II; Ar, X and Ybeing as previously defined. ##STR16##

The reaction is best carried out in inert aprotic organic solvents suchas methylene chloride, tetrahydrofuran or acetonitrile, at ambientpressure and temperature. The mode of addition is not critical; however,it is often convenient to add the sulfonyl isocyanate to a stirredsuspension of the aminopyridine. Since such isocyanates usually areliquids, their addition is more easily controlled.

The reaction is generally exothermic. In some cases, the desired productis insoluble in the warm reaction medium and crystallizes from it inpure form. Products soluble in the reaction medium are isolated byevaporation of the solvent, trituration of the solid residue withsolvents such as 1-chlorobutane, ethyl ether, or pentane, andfiltration.

The intermediate sulfonyl isocyanates of formula II can be prepared byreacting corresponding sulfonamides with phosgene in the presence ofn-butyl isocyanate at reflux in a solvent such as chlorobenzene,according to the procedure of H. Ulrich and A. A. Y. Sayigh, NewerMethods of Preparative Organic Chemistry, Vol. VI p. 223-241, AcademicPress, New York and London, W. Foerst Ed. In cases where formation ofthe desired sulfonyl isocyanate is difficult by the above procedure thesulfonyl urea formed by reaction of butyl isocyanate with theappropriate sulfonamide is treated with phosgene according to the abovereference.

Some of the sulfonyl isocyanates used in this invention are novel. Thesynthesis of these intermediates is described in my co-pendingapplications U.S. Ser. No. 029,281 filed Apr. 13, 1979, U.S. Ser. No.083,753 filed Oct. 22, 1979, and U.S. Ser. No. 098,723 filed Nov. 30,1979, the disclosure of which is herein incorporated by reference.

These intermediates are prepared from the parent sulfonamides of formulaIV as shown in Equation II by reaction with phosgene as described aboveor in my copending application. ##STR17##

A mixture of the appropriate sulfonamide, IIa, an alkyl isocyanate suchas butyl isocyanate and a catalytic amount of1,4-diaza[2,2,2]bicyclooctane (DABCO) in xylene, chlorobenzene or otherinert solvent of sufficiently high boiling point (e.g. >135°) is heatedto approximately 135°. Phosgene is added to the mixture until an excessof phosgene is present as indicated by a drop in the boiling point. (Themixture is heated further to drive off the excess phosgene). After themixture is cooled and filtered to remove a small amount of insolubleby-products, the solvent and alkyl isocyanate are distilled off in-vacuoleaving a residue which is the crude sulfonyl isocyanate II.

In Equation II, R₁ and R₂ are as previously defined.

The preparation of sulfonamides from ammonium hydroxide and sulfonylchlorides is widely reported in the literature, e.g. Crossley et al., J.Am. Chem. Soc. 60, 2223 (1938).

Certain sulfonyl chlorides are best prepared by chlorosulfonation of asubstituted benzene according to the teaching of H. T. Clarke, et al.,Org. Synth. Coll. Vol. 1, 2nd Ed. 1941, p. 85. Other benzenesulfonylchlorides are best made by diazotization of the appropriate aniline withsodium nitrite in HCl, followed by reaction of the diazonium salt withsulfur dioxide and cuprous chloride in acetic acid according to theteaching of H. L. Yale and F. Sowinski, J. Org. Chem. 25, 1824 (1960).

N,N-Dialkyl-o-sulfamoylbenzenesulfonyl isocyanates are importantintermediates for the preparation of certain of the compounds of thisinvention. The synthesis of the sulfonamide intermediates required forthese sulfonyl isocyanates is described in Equation III. ##STR18##wherein R₂, R₅ and R₆ are as previously defined.

In step IIIa, the o-nitrobenzenesulfonyl chloride in formula IV, whichare well-known in the art, are contacted with an amine of formula V inan inert organic solvent such as methylene chloride, ethyl ether, ortetrahydrofuran at 0°-50°. The amine V may be taken in excess to act asan acid acceptor; or, alternatively, a tertiary amine such astriethylamine or pyridine may be used as an acid acceptor. Theby-product amine hydrochloride is filtered off or washed out of thesolvent with water and the product isolated by evaporation of thesolvent.

The reduction described in step IIIb is accomplished by treating asolution of the compounds of formula VI, in a solvent such as ethanol,ethyl acetate, or DMF, in a pressure vessel, with 100-1000 pounds persquare inch or hydrogen at 80°-150° in the presence of a hydrogenationcatalyst such as 5-10% palladium absorbed on carbon. When thetheoretical amount of hydrogen has been absorbed, the solution is cooledand the catalyst is removed by filtration. The product is then isolatedby evaporation of the solvent.

The diazotization and coupling with sulfur dioxide, described in stepIIIc, is accomplished in the following manner. A solution of theo-sulfamoyl aniline of formula VII in a mixture of concentratedhydrochloric acid and glacial acetic acid is treated with a solution ofsodium nitrite in water at -5° to 0°. After stirring for 10-15 minutesat 0° to insure complete diazotization, this solution is added to amixture of an excess of sulfur dioxide, and a catalytic amount ofcuprous chloride in glacial acetic acid at 0°-5°. The temperature iskept at 0°-5° for 1/4 to 1 hour then raised to 20°-25° and held at thattemperature for 2-4 hours. This solution is then poured into a largeexcess of ice water. The sulfonyl chloride products, VIII, can beisolated by filtration or by extraction into a solvent such as ethylether or methylene chloride followed by evaporation of the solvent.

The amination described in step IIId is conveniently carried out bytreating a solution of the sulfonyl chloride of formula VIII with anexcess of anhydrous ammonia in a solvent such as ethyl ether ormethylene chloride at 0°-25°. If the product sulfonamide, IIb, isinsoluble it may be isolated by filtration followed by washing out thesalts with water. If the product sulfonamide is soluble in the reactionsolution, it may be isolated by filtering off the precipitated ammoniumchloride and evaporation of the solvent.

The synthesis of aminoheterocyclics has been reviewed in "The Chemistryof Heterocyclic Compounds," a series published by Interscience Publ.,New York and London. 2-Aminopyridines are described in the volumes ofthis series entitled "Pyridine and Its Derivatives", 1962, edited by E.Klingsberg.

2-Amino-6-bromo-4-methylpyridine and similarly substituted pyridines canbe made by the cyclization of the corresponding dinitrile according tothe teachings of F. Johnson, J. P. Panilla, A. A. Carlson and D. H.Hunneman (J. Org. Chem. 27 2473 (1962)).

Agriculturally suitable salts of compounds of formula I are also usefulherbicides and can be prepared in a number of ways known to the art. Forexample, metal salts can be made by contacting compounds of formula Iwith a solution of an alkali or alkaline earth metal salt having asufficiently basic anion (e.g. hydroxide, alkoxide, carbonate orhydride). Quaternary amine salts can be made by similar techniques.

Salts of compounds of formula I can also be prepared by exchange of onecation for another. Cationic exchange can be effected by direct contactof an aqueous solution of a salt of a compound of formula I (e.g. alkalior quaternary amine salt) with a solution containing the cation to beexchanged. This method is most effective when the desired saltcontaining the exchanged cation is insoluble in water and can beseparated by filtration.

Exchange may also be effected by passing an aqueous solution of a saltof a compound of formula I (e.g. an alkali metal or quaternary aminesalt) through a column packed with a cation exchange resin containingthe cation to be exchanged. In this method, the cation of the resin isexchanged for that of the original salt and the desired produce iseluted from the column. This method is particularly useful when thedesired salt is water-soluble.

Acid addition salts, useful in this invention, can be obtained byreacting a compound of formula I with a suitable acid, e.g.p-toluenesulfonic acid, trichloroacetic acid or the like.

The compounds of this invention and their preparation are furtherillustrated by the following examples wherein temperatures are given indegrees centigrade and parts are by weight unless otherwise designated.

EXAMPLE 1 o-Nitro-N,N-diethylbenzenesulfonamide

To a solution of 132.6 g of o-nitrobenzenesulfonyl chloride in 700 ml oftetrahydrofuran was added 88.5 g of diethylamine at 5°-15°. The reactionmixture was stirred at room temperature for 1 hour before theprecipitated diethylamine hydrochloride was removed by filtration. Thefiltrate was evaporated to dryness in-vacuo and the residue dissolved in1-chlorobutane. The 1-chlorobutane solution was washed with water, driedover magnesium sulfate and evaporated in-vacuo to give 122.4 g ofo-nitro-N,N-diethylbenzenesulfonamide as a dark oil.

NMR(CDCl₃)δ: 1.1-1.4 [t, 6.1H, (CH₃ CH₂)₂ N--]; 3.3-3.8 [qt, 3.8H, (CH₃CH₂)₂ N--]; 8.0-8.6 (m, 4.1H, 4 aromatics).

EXAMPLE 2 o-Amino-N,N-diethylbenzenesulfonamide

In a pressure vessel a mixture of 133 g ofo-nitro-N,N-diethylbenzenesulfonamide, 5 g of 10% palladium on carbon,and 500 ml of ethyl acetate was shaken at 130° under 500 psi hydrogenpressure until hydrogen was no longer absorbed. The reaction mixture wascooled and the catalyst filtered off. Evaporation of the solventin-vacuo gave 123 g of o-amino-N,N-diethylbenzenesulfonamide as aviscous oil which slowly crystallized to a solid, m.p. 45°-51°.

NMR(CDCl₃)δ: 1.0-1.3 [t, 6.7H, (CH₃ CH₂)₂ N--]; 3.0-3.5 [qt, 3.6H, (CH₃CH₂)₂ N--]; 4.8-5.2 (broad, 1.7H, NH₂); 6.5-7.7 (m, 4.0H, 4 aromatics).

EXAMPLE 3 N,N-Diethyl-1,2-benzenedisulfonamide

To a solution of 114 g of o-amino-N,N-diethylbenzenesulfonamide in amixture of 400 ml of concentrated hydrochloric acid and 100 ml ofglacial acetic acid was added a solution of 50 g of sodium nitrite in130 ml of water at -5° to 0°. The solution was stirred at 0° for 15minutes then poured into a mixture of 14 g of cuprous chloride and 100ml of liquid sulfur dioxide in 550 ml of glacial acetic acid at 0°-5°.This mixture was stirred at 0° for 15 minutes then at room temperaturefor 3 hours before pouring into three liters of ice water. The crudesulfonyl chloride was filtered off and washed with water. It was thendissolved in 1 l of ethyl ether, washed with water and dried overmagnesium sulfate. To this ether solution was added 20 ml of liquidanhydrous ammonia at 5°-15°. After stirring overnight at roomtemperature the solid was filtered off, washed with water, ethanol andthen 1-chlorobutane. Oven drying at 60° gave 91.8 gN,N-diethyl-1,2-benzenedisulfonamide, m.p. 156°-9°.

NMR(DMSO)δ: 0.9-1.2 [t, 6.0H, (CH₃ CH₂)₂ N--]; 3.2--3.6 [qt, 3.8H, (CH₃CH₂)₂ N--]; ˜7.2 (broad singlet, 2.1H, NH₂); 7.7-8.4 (m, 4.1H, 4aromatics).

EXAMPLE 4 o-N,N-Diethylsulfonamoylbenzenesulfonyl isocyanate

A solution of 13.2 g of N,N-diethyl-1,2-benzenedisulfonamide, 4.5 g ofn-butylisocyanate, and 0.2 g of 1,4-diaza[2,2,2]bicyclooctane (DABCO) in90 ml of mixed xylenes was heated to 135°. To this solution was added3.3 ml of liquid phosgene at such a rate that the temperature wasmaintained between 125° and 135° (about 2 hours). The temperature waskept at 130° for 1/2 hour after the addition. The solution was cooledand filtered to remove a small amount of insoluble solid thenconcentrated at 60°-70° in-vacuo. The residue ofo-N,N-diethylsulfamoylbenzenesulfonyl isocyanate was an oil weighing16.8 g and was sufficiently pure for further reaction.

EXAMPLE 5 Methyl 2-(isocyanatosulfonyl)benzoate

A stirred mixture containing 157 g of methyl 2-sulfamoylbenzoate, 73 gof butyl isocyanate 0.3 g of 1,4-diazabicyclo[2,2,2,]octane and 1.0 l ofxylene was heated to reflux for one half hour. Phosgene gas was thenpassed into the system under a dry ice reflux condenser allowing thereaction temperature to drop to 120°. This addition was continued untilthe reflux temperature remained at 120° without further phosgeneaddition. The temperature of the reaction mixture was then raised to136° (by removal of the dry ice reflux condenser) after which it wascooled to room temperature and filtered. Evaporation of the filtrateyielded the desired crude sulfonyl isocyanate which could be purified bydistillation at 132°-138° C. under 1.0 to 1.1 mm of mercury pressure.The product is extremely reactive with water so contact with moistureshould be scrupulously avoided.

EXAMPLE 62-[[(4,6-dimethyl-2-pyridinyl)aminocarbonyl]aminosulfonyl]benzoic acid,methyl ester

To 1.2 g of 2-amino-4,6-dimethylpyridine in 30 ml of methylene chlorideat ambient temperature was added dropwise, with stirring 2.4 g of methyl2-isocyanatosulfonylbenzoate. After stirring for one hour at roomtemperature a solid precipitated from the mixture. Filtration yielded1.8 g of a crystalline white solid which melted at 181°-182° C. andshowed absorption peaks by infrared spectroscopy at 1750, 1700, 1630 and1580 cm⁻¹. The nuclear magnetic resonance spectrum (60 mc) showed peaksat 7-8.6 δ (multiplet) for o-substituted benzene, 4.36 δ (singlet) forOCH₃ and 2.76, 2.7 δ (singlets) for the two methyl groups on thepyridine ring.

By using the procedure of Example 6 and substituting equivalent amountsof an appropriately substituted arylsulfonyl isocyanate andaminopyridine, the following compounds are prepared.

                  TABLE I                                                         ______________________________________                                         ##STR19##                                                                                                           m.p.                                   R.sub.1        R.sub.2                                                                              X        Y       (°C.)                           ______________________________________                                        CO.sub.2 CH.sub.3                                                                            H      CH.sub.3 CH.sub.3                                                                              181-                                                                          182°                            CO.sub.2 CH.sub.2 CH.sub.3                                                                   H      CH.sub.3 CH.sub.3                                       CO.sub.2 CH.sub.2 CH.sub.2 CH.sub.3                                                          H      CH.sub.3 CH.sub.3                                        ##STR20##     H      CH.sub.3 CH.sub.3                                       CO.sub.2 CH.sub.2 CH.sub.2 CH.sub.2 CH.sub.2                                                 H      CH.sub.3 CH.sub.3                                        ##STR21##     H      CH.sub.3 CH.sub.3                                       CO.sub.2CH.sub.2 CHCH.sub.2                                                                  H      CH.sub.3 CH.sub.3                                       CO.sub.2CH.sub.2 CHCH.sub.2 CH.sub.3                                                         H      CH.sub.3 CH.sub.3                                       CO.sub.2 CH.sub.2 CH.sub.2 Cl                                                                H      CH.sub.3 CH.sub.3                                       CO.sub.2 CH.sub. 2 CH.sub.2 OCH.sub.3                                                        H      CH.sub.3 CH.sub.3                                       CF.sub.3       H      CH.sub.3 CH.sub.3                                       NO.sub.2       H      CH.sub.3 CH.sub.3                                                                              162°                                                                   (d)                                    Cl             H      CH.sub.3 CH.sub.3                                       SO.sub.2 CH.sub.3                                                                            H      CH.sub.3 CH.sub.3                                       SO.sub.2 CH.sub.2 CH.sub.3                                                                   H      CH.sub.3 CH.sub.3                                       SO.sub.2 CH.sub.2 CH.sub.2 CH.sub.3                                                          H      CH.sub.3 CH.sub.3                                                                              188-                                                                          189°                             ##STR22##     H      CH.sub.3 CH.sub.3                                       SO.sub.2 CH.sub.2 CH.sub.2 CH.sub.2 CH.sub.3                                                 H      CH.sub.3 CH.sub.3                                        ##STR23##     H      CH.sub.3 CH.sub.3                                       SO.sub.2 N(CH.sub.3).sub.2                                                                   H      CH.sub.3 CH.sub.3                                                                              204-                                                                          210°                             ##STR24##     H      CH.sub.3 CH.sub.3                                       SO.sub.2 N(CH.sub.2 CH.sub.3).sub.2                                                          H      CH.sub.3 CH.sub.3                                       Cl             Cl     CH.sub.3 CH.sub.3                                       Cl             CH.sub.3                                                                             CH.sub.3 CH.sub.3                                       NO.sub.2       CH.sub.3                                                                             CH.sub.3 CH.sub.3                                       NO.sub.2       Cl     CH.sub.3 CH.sub.3                                       CO.sub.2 CH.sub.3                                                                            H      CH.sub.3 OCH.sub.3                                                                             184-                                                                          187°                            CO.sub.2 CH.sub.3                                                                            H      CH.sub.3 Br      210-                                                                          211°                            CO.sub.2 CH.sub.3                                                                            H      CH.sub.2 CH.sub.3                                                                      Br      136-                                                                          140°                            CO.sub.2 CH.sub.3                                                                            H      CH.sub.2 CH.sub.3                                                                      OCH.sub.3                                                                             184-                                                                          188°                            CO.sub.2 CH.sub.3                                                                            H      OCH.sub.3                                                                              OCH.sub.3                                      CO.sub.2 CH.sub.3                                                                            H      CH.sub.3 OCH.sub.2 CH.sub.3                             CO.sub.2 CH.sub.3                                                                            H      CH.sub.3 Cl                                             CO.sub.2 CH.sub.3                                                                            H      CH.sub.3 F                                              CO.sub.2 CH.sub.3                                                                            H      CH.sub.2 CH.sub.3                                                                      CH.sub.2 CH.sub.3                              SO.sub.2 N(CH.sub.3).sub.2                                                                   H      OCH.sub.3                                                                              CH.sub.3                                       SO.sub.2 N(CH.sub.3).sub.2                                                                   H      OCH.sub.3                                                                              CH.sub.2 CH.sub.3                              ______________________________________                                    

                  TABLE II                                                        ______________________________________                                         ##STR25##                                                                    R.sub.3  X           Y          m.p. (°C.)                             ______________________________________                                        Cl       CH.sub.3    CH.sub.3   149-155°                               Cl       CH.sub.3    OCH.sub.3                                                Cl       CH.sub.3    Br                                                       Cl       CH.sub.2 CH.sub.3                                                                         CH.sub.3                                                 Cl       CH.sub.2 CH.sub.3                                                                         OCH.sub.3                                                Cl       CH.sub.2 CH.sub.3                                                                         Br                                                       Cl       OCH.sub.3   OCH.sub.3                                                Cl       OCH.sub.3   CH.sub.3                                                 Cl       CH.sub.3    Cl                                                       Cl       CH.sub.2 CH.sub.3                                                                         CH.sub.2 CH.sub.3                                        ______________________________________                                    

                  TABLE III                                                       ______________________________________                                         ##STR26##                                                                    R.sub.4          X           Y                                                ______________________________________                                        CH.sub.3         CH.sub.3    CH.sub.3                                         CH.sub.2 CH.sub.3                                                                              CH.sub.3    CH.sub.3                                         CH.sub.2 CH.sub.2 CH.sub.3                                                                     CH.sub.3    OCH.sub.3                                         ##STR27##       CH.sub.3    OCH.sub.3                                        CH.sub.2 CH.sub.2 CH.sub.2 CH.sub.3                                                            CH.sub.3    Br                                                ##STR28##       CH.sub.2 CH.sub.3                                                                         OCH.sub.3                                         ##STR29##       CH.sub.2 CH.sub.3                                                                         Br                                               ______________________________________                                    

Formulations

Useful formulations of the compounds of Formula I can be prepared inconventional ways. They include dusts, granules, pellets, suspensions,emulsions, wettable powders, emulsifiable concentrates and the like.Many of them can be applied directly. Sprayable formulations can beextended in suitable media and used at spray volumes of from a fewliters to several hundred liters per hectare. High strength compositionsare used primarily as concentrates which are to be diluted prior toultimate use. The formulations, broadly, contain about 0.1% to 99% byweight of active ingredient(s) and at least one of (a) about 0.1% to 20%surfactant(s) and (b) about 1% to 99.9% solid or liquid diluent(s). Morespecifically, they will contain these ingredients in the approximateproportions set forth in Table II.

                  TABLE IV                                                        ______________________________________                                                       Weight Percent*                                                               Active            Surfac-                                                     Ingredient                                                                            Diluent (s)                                                                             tant (s)                                     ______________________________________                                        Wettable Powders 20-90      0-74     1-10                                     Oil Suspensions, Solutions                                                    Emulsions                                                                     (including                                                                    Emulsifiable                                                                  Concentrates)    5-50      40-95     0-15                                     Aqueous Suspensions                                                                            10-50     40-84     1-20                                     Dusts            1-25      70-99     0-5                                      Granules and Pellets                                                                           0.1-95      5-99.9  0-15                                     High Strength Compositions                                                                     90-99      0-10     0-2                                       *Active Ingredient plus at least one of a Surfactant or a Diluent equals      100 weight percent.                                                      

Lower or higher levels of active ingredient can be present, depending onthe intended use and the physical properties of the compound. Higherratios of surfactant to active ingredient are sometimes desirable, andare achieved by incorporation into the formulation, or by tank mixing.

Some typical solid diluents are described in Watkins, et al., "Handbookof Insecticide Dust Diluents and Carriers", 2nd Ed., Dorland Books,Caldwell, N.J., but other solids, either mined or manufactured, may beused. The more absorptive diluents are preferred for wettable powdersand the denser ones for dusts. Typical liquid diluents and solvents aredescribed in Marsden, "Solvents Guide", 2nd Ed., Interscience, New York,1950. Solubility under 0.1% is preferred for suspension concentrates;solution concentrates are preferably stable against phase separation at0° C. "McCutcheon's Detergents and Emulsifiers Annual", MC PublishingCorp., Ridgewood, N.J., as well as Sisely and Wood, "Encyclopedia ofSurface Active Agents", Chemical Publishing Co., Inc., New York, 1964,list surfactants and recommended uses. All formulations can containminor amounts of additives to reduce foaming, caking, corrosion,microbiological growth, etc.

The methods of making such compositions are well known. Solutions areprepared by simply mixing the ingredients. Fine solid compositions aremade by blending, and usually grinding, as in a hammer or fluid energymill. Suspensions are prepared by wet milling (see, for example,Littler, U.S. Pat. No. 3,060,084). Granules and pellets can be made byspraying the active material on preformed granular carriers or byagglomeration techniques. See J. E. Browning, "Agglomeration", ChemicalEngineering, Dec. 4, 1967, pp. 147ff. and "Perry's Chemical Engineer'sHandbook", 4th Ed., McGraw-Hill, New York, 1963, pp. 8-59ff.

For further information regarding the art of formulation, see forexample:

H. M. Loux, U.S. Pat. No. 3,235,361, Col. 6, line 16 through Col. 7,line 19 and Examples 10 through 41.

R. W. Luckenbaugh, U.S. Pat. No. 3,309,192, Col. 5, line 43 through Col.7, line 62 and Examples 8, 12, 15, 39, 41, 52, 53, 58, 132, 138-140,162-164, 166, 167, 169-182.

H. Gysin and E. Knusli, U.S. Pat. No. 2,891,855, Col. 3, line 66 throughCol. 5, line 17 and Examples 1-4.

G. C. Klingman, "Weed Control as a Science", John Wiley & Sons, Inc.,New York, 1961, pp. 81-96.

J. D. Fryer and S. A. Evans, "Weed Control Handbook", 5th Ed., BlackwellScientific Publications, Oxford, 1968, pp. 101-103.

Unless indicated otherwise, all parts are by weight in the followingexamples.

EXAMPLE 7 Wettable Powder

    ______________________________________                                        2-[[(4,6-dimethyl-2-pyridinyl)-                                               aminocarbonyl]aminosulfonyl]-                                                 benzoic acid, methyl ester                                                                          80%                                                     sodium alkylnaphthalenesulfonate                                                                    2%                                                      sodium ligninsulfonate                                                                              2%                                                      synthetic amorphous silica                                                                          3%                                                      kaolinite             13%                                                     ______________________________________                                    

The ingredients are thoroughly blended and hammer milled to produceparticles essentially all below 50 microns. The product is reblended andsifted through a U.S.S. No. 50 sieve (0.3 mm opening) before packaging.

EXAMPLE 8 Wettable Powder

    ______________________________________                                        2-[[(4,6-dimethyl-2-pyridinyl)-                                               aminocarbonyl]aminosulfonyl]-                                                 benzoic acid, methyl ester                                                                          50%                                                     sodium alkylnaphthalenesulfonate                                                                    2%                                                      low viscosity methyl cellulose                                                                      2%                                                      diatomaceous earth    46%                                                     ______________________________________                                    

The ingredients are blended, coarsely hammer milled and then air milledto produce particles of active essentially all below 10 microns indiameter. The product is reblended before packaging.

EXAMPLE 9 Granule

    ______________________________________                                        wettable powder of Example 8                                                                       10%                                                      attapulgite granules 90%                                                      (U.S.S. #20-40; 0.84-0.42 mm)                                                 ______________________________________                                    

A slurry of wettable powder containing 50% solids is sprayed on thesurface of attapulgite granules in a double-cone blender. The granulesare dried and packaged.

EXAMPLE 10 Oil Suspension

    ______________________________________                                        2-[[(4,6-dimethyl-2-pyridinyl)-                                               aminocarbonyl]aminosulfonyl]-                                                 benzoic acid, methyl ester                                                                           25%                                                    polyoxyethylene sorbitol hexaoleate                                                                   5%                                                    highly aliphatic hydrocarbon oil                                                                     70%                                                    ______________________________________                                    

The ingredients are ground together in a sand mill until the solidparticles have been reduced to under about 5 microns. The resultingthick suspension may be applied directly, but preferably after beingextended with oils or emulsified in water.

EXAMPLE 11 Wettable Powder

    ______________________________________                                        2-[[(4,6-dimethyl-2-pyridinyl)-                                               aminocarbonyl]aminosulfonyl]-                                                 benzoic acid, methyl ester                                                                          65%                                                     dodecylphenol polyethylene glycol                                             ether                 2%                                                      sodium ligninsulfonate                                                                              4%                                                      sodium silicoaluminate                                                                              6%                                                      montmorillonite (calcined)                                                                          23%                                                     ______________________________________                                    

The ingredients are thoroughly blended. The liquid surfactant is addedby spraying upon the solid ingredients in the blender. After grinding ina hammer mill to produce particles essentially all below 100 microns,the material is reblended and sifted through a U.S.S. No. 50 sieve (0.3mm opening) and packaged.

EXAMPLE 12 High Strength Concentrate

    ______________________________________                                        2-[[(4,6-dimethyl-2-pyridinyl)-                                               aminocarbonyl]aminosulfonyl]-                                                 benzoic acid, methyl ester                                                                         98.5%                                                    silica aerogel       0.5%                                                     synthetic amorphous fine silica                                                                    1.0%                                                     ______________________________________                                    

The ingredients are blended and ground in a hammer mill to produce ahigh strength concentrate essentially all passing a U.S.S. No. 50 sieve(0.3 mm openings). This material may then be formulated in a variety ofways.

EXAMPLE 13 Extruded Pellet

    ______________________________________                                        2-[[(4,6-dimethyl-2-pyridinyl)-                                               aminocarbonyl]aminosulfonyl]-                                                 benzoic acid, methyl ester                                                                          25%                                                     anhydrous sodium sulfate                                                                            10%                                                     crude calcium ligninsulfonate                                                                        5%                                                     sodium alkylnaphthalenesulfonate                                                                     1%                                                     calcium/magnesium bentonite                                                                         59%                                                     ______________________________________                                    

The ingredients are blended, hammer milled and then moistened with about12% water. The mixture is extruded as cylinders about 3 mm diameterwhich are cut to produce pellets about 3 mm long. These may be useddirectly after drying, or the dried pellets may be crushed to pass aU.S.S. No. 20 sieve (0.84 mm openings). The granules held on a U.S.S.No. 40 sieve (0.42 mm openings) may be packaged for use and the finesrecycled.

EXAMPLE 14 Wettable Powder

    ______________________________________                                        2-[[(4,6-dimethyl-2-pyridinyl)-                                               aminocarbonyl]aminosulfonyl]-                                                 benzoic acid, methyl ester                                                                         40%                                                      dioctyl sodium sulfosuccinate                                                                      1.5%                                                     sodium ligninsulfonate                                                                             3%                                                       low viscosity methyl cellulose                                                                     1.5%                                                     attapulgite          54%                                                      ______________________________________                                    

The ingredients are thoroughly blended, passed through an air mill, toproduce an average particle size under 15 microns, reblended, and siftedthrough a U.S.S. No. 50 sieve (0.3 mm opening) before packaging.

All compounds of the invention may be formulated in the same manner.

Utility

The compounds of formula I are useful as herbicides. They may be appliedeither pre- or post-emergence for the control of undesired vegetation innoncrop areas or for selective weed control in certain crops, e.g.,wheat. Some of these compounds are useful for the pre- and/orpost-emergence control of nutsedge. By properly selecting rate and timeof application, compounds of this invention may be used to modify plantgrowth beneficially.

The precise amount of the compound of formula I to be used in any givensituation will vary according to the particular end result desired, theuse involved, the weeds to be controlled, the soil type, the formulationand mode of application, weather conditions, etc. Since so manyvariables play a role, it is not possible to state a rate of applicationsuitable for all situations. Broadly speaking, the compounds of thisinvention are used at levels of about 0.01 to 20 kg/ha with a preferredrange of 0.05 to 10 kg/ha. The lower rates of the range will generallybe selected for lighter soils, for selective weed control in crops, orin situations where maximum persistence is not necessary. Some of thecompounds of formula I can be used at very low rates for plant growthmodification, but higher rates may also be useful, depending on factorssuch as the crop being treated, timing of treatment, etc.

Combinations of the compounds of Formula I with known herbicides alsoprovide effective control of weeds in small grain crops such as wheatand barley. Typical herbicides that may be used are chlortoluron[3-(3-chloro-4-methylphenyl)-1,1-dimethylurea], MCPP[(±)-2-(4-chloro-2-methylphenoxy)propanoic acid], metoxuron[3-(3-chloro-4-methoxyphenyl)-1,1-dimethylurea], methabenzthiazuron[1-(benzothiazol-2-yl)-1,3-dimethylurea], dichlofop[(methyl-2-[4-(2,4-dichlorophenoxy)phenoxy]propanoate)],tri-allate[S-2,3-dichloroallyl di-isopropylthiocarbamate],isoproturon[3-(4-isopropylphenyl)-1,1-dimethylurea], ordifenzoquat[1,2-dimethyl-3,5-diphenylpyrazolium ion].

The compounds of Formula I may also be combined with other herbicidesand are particularly useful in combination with ureas, such as3-(3,4-dichlorophenyl)-1,1-dimethylurea,3-(3,4-dichlorophenyl)-1-methoxy-1-methylurea and1,1-dimethyl-3-(α,α,α-trifluoro-m-tolyl)urea; the triazines such as2-chloro-4-(ethylamino)-6-(isopropylamino)-s-triazin; the uracils suchas 5-bromo-3-sec-butyl-6-methyluracil; N-(phosphonomethyl)glycine;3-cyclohexyl-1-methyl-6-dimethylamino-s-triazine-2,4(1H,3H)-dione;N,N-dimethyl-2,2-diphenylacetamide; 2,4-dichlorophenoxyacetic acid (andclosely related compounds); 4-chloro-2-butynyl-3-chlorophenylcarbamate;diisopropylthiolcarbamic acid, S-(2,3,3-trichloroally)ester;ethyl-N-benzoyl-N-(3,4-dichlorophenyl)-2-aminopropionate;4-amino-6-tert-butyl-3-(methylthio)-1,2,4-triazin-5(4H)-one;3-isopropyl-1H-2,1,3-benzothiodiazin-(4)-3H-one-2,2-dioxide;α,α,α-trifluoro-2,6-dinitro-N,N-dipropyl-p-toluidine;1,1'-dimethyl-4,4'-bipyridinium ion; monosodium methanearsonate; and2-chloro-2',6'-diethyl(methoxymethyl)acetanilide.

The activity of these compounds was discovered in a number of greenhousetests. The tests are described and the data resulting from them areshown below. The ratings are based on a numerical scale extending from0=no effect, to 10=maximum effect. The accompanying descriptive symbolshave the following meanings:

    ______________________________________                                                C = chlorosis or necrosis                                                     D = defoliation                                                               E = emergence inhibition                                                      G = growth retardation                                                        H = formative effects                                                         6Y = abscised flowers or buds                                                 6F = delayed flowering                                                        S = albinism                                                          ______________________________________                                    

TEST A

Seeds of crabgrass (Digitaria spp.), barnyardgrass (Echinochloacrusgalli), wild oats (Avena fatua), cassia (Cassia tora), morningglory(Ipomoea spp.), cocklebur (Xanthium spp.), sorghum, corn, soybean, rice,wheat and nutsedge tubers (Cyperus rotundus) were planted in a growthmedium and treated preemergence with a nonphytotoxic solvent solution ofthe compound of Table III. Other batches of seeds and tubers for all ofthe foregoing weed and crop plants were planted at the same time ascontrols. The control plantings were untreated; i.e., neither anycompound nor any solvent was applied. At the same time, cotton havingfive leaves (including cotyledonary ones), bush beans with the thirdtrifoliate leaf expanding, crabgrass with two leaves, barnyardgrass withtwo leaves, wild oats with two leaves, cassia with three leaves(including cotyledonary ones), morningglory with four leaves (includingthe cotyledonary ones), cocklebur with four leaves (including thecotyledonary ones), sorghum with four leaves, corn with four leaves,soybean with two cotyledonary leaves, rice with three leaves, wheat withone leaf, and nutsedge with three-five leaves were sprayed with anonphytotoxic solvent solution of the compound of Table III. Othergroups of all the same weed and crop plants were sprayed with the samenonphytotoxic solvent so as to provide control plants. Preemergence andpostemergence treated plants and controls were maintained in agreenhouse for sixteen days, then all treated plants were compared withtheir respective controls and rated visually for response to treatment.The data in Table A shows that the compounds of this invention areeffective as herbicides.

    TABLE A      POST-EMERGENCE          BARN-         BUSH-  MORNING- COCKLE-  NUT-     CRAB- YARD- WILD   SOY-  SOR-  kg/ha BEAN COTTON GLORY BUR CASSIA SEDGE     GRASS GRASS OATS WHEAT CORN BEAN RICE GHUM      ##STR30##      2/5 9C 6C,9G 10C 9C 5C,9G 1C,9G 1C,5G 1C,3H 0 0 1C,5G 9C 5C,7G 2C,9H      ##STR31##      2/5 1C 2C 3C,9G 1C 0 1C 3G 0 0 0 0 2C,7G 1C 0      ##STR32##      2/5 2C,6G,6Y 3C,3H,5G 3C,5H 0 2C,4G 0 0 2C 0 0 2G 4C,9G 4C,8G 2C,7G      ##STR33##      2 5S,9G,6Y 2C 2C 2C,2H,6F 2C,5G 0 0 0 0 0 0 2G 0 0      ##STR34##      2 5C,6Y,9G 3C,3H 2C 2C,3H 2C 5G 1C 2C,6H 1C 0 3C 3C 0 2C,8H      ##STR35##      2/5 9C 7C,9G 1C,5G 5G 3C,8H 2G 1C,5G 2C,8H 2C,5G 1C,3G 1C,6H 5C,9G     3C,9G 5C,8G      ##STR36##      0.42 9D,9G3C,9D,9G 4C,5H3C,3H,8G 8G3C,9G 8G1C,8G 2C,8H2C,9G 2C,8G8G     3G4G 2C,8H2C,9H 2C3C,5G 1C3G 9H9H 4C,9G9C 2C,9G5C,8G 1C,9G2C,9G       PRE-EMERGENCE        BARN-         MORNING- COCKLE-  NUT- CRAB- YARD-     WILD   SOY-  SOR-  kg/ha GLORY BUR CASSIA SEDGE GRASS GRASS OATS WHEAT     CORN BEAN RICE GHUM      ##STR37##      2/5 9C 9H 5C,9G 10E 2C 3C,6G 3G 3G 8H 9H 10E 9H      ##STR38##      2/5 9C 9H 0 0 0 0 0 0 2G 1C 2G 1C      ##STR39##      2/5 7G 8G 2C 5G 2C 1C,6G 5G 3G 2C,7G 2C,6H 3C,8H 2C,8G      ##STR40##      2 5H 0 -- 0 0 0 0 0 0 2G 1C 0      ##STR41##      2 9G 8H 5C,7G -- 1C,7G 5C,9H 4C,7H 2C,7G 1C,9G 3C,5H 10E 2C,9H      ##STR42##      2/5 9G 9H 9G 10E 2C,5G 3C,9H 2C,8G 1C,6G 9H 9H 10E 10H      ##STR43##      0.42 9G9G --9G 9G5C,9G 10E10E 2G4G 2C,9H9H 1C,8G8G 6G8G 9G9H 9H9H 9H10E 2     C,9H9H

TEST B

Two bulb pans were filled with fertilized and limed Fallsington siltloam soil. One pan was planted with seeds of corn, sorghum, Kentuckybluegrass and several grassy weeds. The other pan was planted with seedsof soybeans, purple nutsedge tubers (Cyperus rotundus), and seeds ofseveral broadleaf weeds. Seeds of the following grassy and broadleafweeds were planted: crabgrass (Digitaria sanguinalis), barnyardgrass(Echinochloa crusgalli), wild oats (Avena fatua), johnsongrass (Sorghumhalepense), giant foxtail (Setaria faberii), dallisgrass (Paspalumdilatatum), cheatgrass (Bromus secalinus), mustard (Brassica arvensis),cocklebur (Xanthium pennsylvanicum), pigweed (Amaranthus retroflexus),morningglory (Ipomoea hederacea), cassia (Cassia tora), teaweed (Sidaspinosa), velvetleaf (Abutilon theophrasti), and jimsonweed (Daturastramonium). A smaller pot was filled with prepared soil and plantedwith rice and wheat seeds. Another small pot was planted with seeds ofsugarbeets. The above four containers were treated preemergence withnonphytotoxic solvent solutions of a compound of this invention (i.e.,solutions of said compound were sprayed on the soil surface before seedgermination). Duplicates of the above-described seeded containers wereprepared without treatment and used as controls.

Twenty-eight days after treatment, the treated and control plants wereevaluated and the data recorded as set forth in Table B.

    TABLE B      PRE-EMERGENCE ON FALLSINGTON SILT LOAM          Barn-             Rate Crab- yard-  Wild Johnson- Dallis- Giant Ky.     Blue- Cheat- Sugar-   Cockle-  kg/ha grass grass Sorghum Oats grass     grass Foxtail grass grass beets Corn Mustard bur      ##STR44##      1/161/4 00 03G 4G8G,5H 00 05H 00 03G 02G 3G5G 3G5G,5C 02G 4G7G 00      ##STR45##      0.060.25 00 02G 8G,3H9G,5H 04G 5G6G 00 00 03G 4G7G,3C 6G8G,8C 02G     10E10E 00      ##STR46##      0.060.25 00 04G 3G8G,5H 03G 06G,3H 00 02G 00 03G 04G 03G 4G8G,5H 00      ##STR47##      0.060.25 00 4G5G,3C 8G,3H10C 5G6G,3C 5G8G,8C 04G 3G4G 5G6G 7G,5E10E     10C10C 03G 8G,8C10C 2G5G        Rate Pig- Nut-  Morning-  Tea- Velvet- Jimson-     kg/ha weed sedge     Cotton glory Cassia weed leaf weed Soybean Rice Wheat      ##STR48##      1/161/4 00 03G 03G 00 00 05G 00 00 05G 06G,5C 03G      ##STR49##      0.060.25 ---- 6G7G,3C 03G 4G7G 6G6G 2G7G 05G 5G8G,8C 2C7G,5H 6G,3C8G,8E 0    0      ##STR50##      0.060.25 05G 00 02G 00 ---- 00 03G 00 02G 03G 00      ##STR51##      0.060.25 10E10E 03G 4G5G,2H 6G7G ---- 5G8G 7G,5H8G,7C 6G7G,3C 3G6G,5H     10E10E 3G5G

TEST C

Pots filled with Fallsington silt loam were planted to soybeans, cotton,corn, rice, wheat, sorghum, alfalfa, velvetleaf (Abutulon theophrasti),sesbania (Sesbania exaltata), cassia (Cassia tora), morningglory(Ipomoea spp.), jimsonweed (Datura stramonium), cocklebur (Xanthiumpennsylvanicum), crabgrass (Digitaria spp.), nutsedge (Cyperus rotunda),barnyardgrass (Echinochloa crusgalli), giant foxtail (Setaria faberii),and wild oats (Avena fatua). Approximately 21/2 weeks after planting,the young plants and the soil around them were sprayed overall with thecompound of Example 1 dissolved in a nonphytotoxic solvent. Other groupsof all the same weed and crop plants were sprayed with the samenonphytotoxic solvent so as to provide control plants. Fourteen daysafter treatment, all treated plants were compared with the nonphytotoxicsolvent controls and visually rated for response to treatment to givethe data presented in Table C.

    TABLE C      Over-the-Top Soil/Foliage Treatment                        Gi-    Rate  Vel-    Morn-  Jim-      Barn-  ant  kg/     Soy- vet Ses-   ing  son- Cockle-  Crab-  Nut- yard-  Fox- Sor- Wild  ha     beans leaf bania Cassia Cotton glory Alfalfa weed bur Corn grass Rice     sedge grass Wheat tail ghum Oats      ##STR52##      1/641/16 9G,5C10G,8C 5G,2C8G,3C 5G,2C7G,4C 04G 5G,2C8G,5C 2G7G 5G5G     3G4G 00 3G3G 00 3G6G 00 5G5G 04G 00 4G,3H 8G,3H 00                         Gi-    Rate  Vel-    Morn-  Jim-      Barn-  ant     kg/ Soy- vet Ses-   ing  son- Cockle-  Crab-  Nut- yard-  Fox- Wild Sor-      ha beans leaf bania Cassia Cotton glory Alfalfa weed bur Corn grass     Rice sedge grass Wheat tail Oats ghum      ##STR53##      1/41/16 10G,7C10G,5C 8G,3C6G,3C 10G,9C10G,9C 7G,4C6G,3C 7G,3C5G,2C      9     9G,6CG,6C 8G,4C7G,3C 7G,3C7G,3C 10G,9C6G 00 2G,1C0 7G,2C6G,1C 9G,4C9G,4C 3     G,2C2G,1C 00 2G0 1G1G 9G,6C 8G,4C      ##STR54##      1/81/32 10G,5C10G,5C 6G,3C5G,2C 10G,8C10G,8C 7G,3C5G,2C 5G,3C4G,2C      6     6G,3CG,3C 3G,1C1C 4G,1C3G,2C 2G,1C1G,1C 00 2C2C 8G,3C8G,1C 2G2G 1G0 00   0     2G 3G0 9G,4C9G,4C

TEST D

A compound within the scope of the invention was highly active againstnutsedge, as is evident from the following test.

Purple nutsedge tubers (Cyperus rotundus) were planted about 2 cm deepin Fallsington silt loam contained in plastic pots 10 cm in diameter.Five tubers were put in each pot. A compound of this invention wassprayed dissolved in a non-phytotoxic solvent at a volume rate of 560l/ha. in four different methods of treatment, i.e., soil surface spray,tuber/soil spray, soil incorporated and post-emergence. For the soilsurface spray, the compound was sprayed on the firmed soil surfaceimmediately after planting. For the tuber/soil spray, the compound wassprayed on the exposed tubers and subtending soil before the untreatedcovering soil was added. The soil incorporation treatment was mixed inthe covering soil. The post-emergence treatment was sprayed on thenutsedge foliage and surrounding soil surface after the nutsedge hademerged and had reached the height of about 12 cm.

Immediately after spraying the surface spray, tuber/soil spray and soilincorporated treatments were misted with about 0.3 cm of water over a 90minute period and then placed in the greenhouse. The post-emergencetreatment was placed directly into the greenhouse and watered carefullyso that the treatment would not be washed from the foliage.

The following Table D gives results 4 weeks after treating nutsedge withthe compound of this invention.

                  TABLE D                                                         ______________________________________                                                1                                                                     Nutsedge Control                                                               ##STR55##                                                                    RESPONSE RATING                                                               Rate  Pre-Emerg. Tuber       Soil    Post-                                    kg/ha Soil Surface                                                                             Spray       Incorp. Emerg.                                   ______________________________________                                        1/64  0          4G          2G      0                                        1/16  2C,6G      8G          9G      4G                                       1/4   4E,9G      8E,9G       9E,9G   3C,6G                                    ______________________________________                                    

TEST E

Two ten-inch in diameter plastic pans lined with polyethylene linerswere filled with prepared Fallsington silt loam soil. One pan wasplanted with seeds of wheat (Triticum aestivum), barley (Hordeumvulgare), wild oats (Avena fatua), downy brome (Bromus tectorum),cheatgrass (Bromus secalinus), blackgrass (Alopecurus myosuroides),annual bluegrass (Poa annua), green foxtail (Setaria viridis),quackgrass (Agropyron repens), Italian ryegrass (Lolium multiflorum) andripgut brome (Bromus rigidus). The other pan was planted with seeds ofwild buckwheat (Polygonum convolvulus), Kochia scoparia, smartweed(Polygonum pensylvanicum), Matricaria inodora, tumble mustard(Sisymbrium altissium), wild mustard (Brassica kaber), tansy mustard(Descurainia pinnata), black nightshade (Solanum nigrum) and Russianthistle (Salsola kali). The above two pans were treated pre-emergence.At the same time, two pans in which the above plant species were growingwere treated post-emergence. Plant height at the time of treatmentranged from 1-15 cm depending on plant species.

The compounds applied were diluted with a non-phytotoxic solvent andsprayed over-the-top of the pans. An untreated control and a solventalone control were included for comparison. All treatments weremaintained in the greenhouse for 20 days at which time the treatmentswere compared to the controls and the effects visually rated. Therecorded data are presented in Table E. It is clear from these data thatseveral of the test compounds have utility for weed control in cerealcrops.

    TABLE E       Rate    Wild Downy Cheat- Black- Annual Green Quack- Italian Ripgut     Russian Tansy  kg/ha  Wheat Barley Oats brome grass grass bluegrass     foxtail grass ryegrass brome thistle mustard      ##STR56##      0.0150.015 Pre-EmergencePost-Emergence 00 00 00 3G2C,3G 5G3C,7G     1C,3G2C,2G 2G3G 01C,4G 00 01G 01G 010C 9C,9G10C      ##STR57##      0.060.06 Pre-EmergencePost-Emergence 00 1G1G 00 3C,4G3C,5G 3C,7G4C,7G     2C,4G2C,3G 5G4G 2C,3G1C,5G 3G2G 1G3G 1G2G 7C,5G10C 10C10C      ##STR58##      0.030.03 Pre-EmergencePost-Emergence 00 2G1G 1G1C,1G 2C,5G2C,3G     3C,6G2C,6G 6G2C,5G 2C,5G1C,3G 2G2G 4G1C,2G 3G1G 3G1G 1G10C  10C10C      ##STR59##      0.1250.125 Pre-EmergencePost-Emergence 00 4G2C,3G 2G1C,2G 7C,6G4C,5G     7C,8G4C,7G 6C,7G3C,6G 3C,6G2C,5G 2C,5G2C,4G 7G1C,3G 2C,6G1C,2G 4G2C,3G     5C,6G10C 10C10C      ##STR60##      0.060.06 Pre-EmergencePost-Emergence 00 00 00 2C,3G1G 4C,6G2G  1C,3G0   0     1G 2C,2G0 00 00 00 10C-- 9C,9G9C,7G      ##STR61##      0.250.25 Pre-EmergencePost-Emergence 00 1C,2G1C,2G 3C,3G0 7C,8G5C,4G     9C,8G4C,4G 5C,7G1C,2G 1C,3G0 2C,3G0 1C,3G0 1C,2G0 1C,2G2C,2G 7C,8G--     9C,9G10C              Matri- Black   Wild  Rate  Smart- Tumble  Shepherd's caria     night- Yellow Wild buck-  kg/ha  weed mustard Kochia purse inodora shade     rocket mustard wheat      ##STR62##      0.0150.015 Pre-EmergencePost-Emergence ---- 10C10C 3G3C,5G 7C,8G2C,3G     3C,7G9C,8G 8G1C,4G 7C,8G10C 7C,8G10C 2C,3G2C,3G      ##STR63##      0.060.06 Pre-EmergencePost-Emergence ---- 10C10C 5G7C,8G 10C3C,3G     8C,9G10C 8G3C,6G 9C,9G10C 9C,9G 10C 5C,6G2C,4G      ##STR64##      0.030.03 Pre-EmergencePost-Emergence ---- 10C10C 3G0 3C,8G7C,6G     5C,8G10C 6G2C,5G 7C,9G10C 7C,8G10C 2C,4G1C,2G      ##STR65##      0.1250.125 Pre-EmergencePost-Emergence ---- 10C10C 3G2C,3G 5C,7G8C,7G     6C,7G10C 7G2C,6G 8G10C 10C 10C 3C,7G2C,4G      ##STR66##      0.060.06 Pre-EmergencePost-Emergence ---- 9C,9G10C 3G7C,8G 3C,6G1C,1G     3C,3G0 2C,6G1G 7C,8G4C,5G 7C,8G10C 2C,1G0      ##STR67##      0.250.25 Pre-EmergencePost-Emergence ---- 9C,9G10C 3C,5G1C,2G 7C,7G2G     7C,8G2C,3G 3C,8G3G 9C,8G7C,8G 9C,8G 10C 6C,7G0

What is claimed is:
 1. A compound of the formula: ##STR68## wherein X isCH₃ --, CH₃ CH₂ -- or CH₃ O;Y is CH₃ --, CH₃ CH₂ --, CH₃ O--, CH₃ CH₂O--, Cl, Br or F; Ar is ##STR69## R₁ is R₅ SO₂ -- or R₆ R₇ NSO₂ --; R₂is H, Cl or CH₃ ; R₃ is Cl; R₄ is C₁ -C₄ alkyl, C₃ -C₄ alkenyl, ClCH₂CH₂ -- or CH₃ OCH₂ CH₂ --; R₅ is C₁ -C₄ alkyl; R₆ and R₇ areindependently CH₃ -- or CH₃ CH₂ --.
 2. A compound of claim 1 wherein R₁is R₆ R₇ NSO₂ --, R₅ SO₂ --, wherein R₄ is C₁ -C₃ alkyl or allyl.
 3. Acompound of claim 1 wherein Y is Cl, Br, CH₃ -- or CH₃ O--.
 4. Acompound of claim 2 wherein Y is Cl, Br, CH₃ -- or CH₃ O--.
 5. Acomposition suitable for controlling the growth of undesired vegetationwhich comprises an effective amount of a compound of claim 1 and atleast one of the following: surfactant, solid or liquid diluent.
 6. Acomposition suitable for controlling the growth of undesired vegetationwhich comprises an effective amount of a compound of claim 2 and atleast one of the following: surfactant, solid or liquid diluent.
 7. Acomposition suitable for controlling the growth of undesired vegetationwhich comprises an effective amount of a compound of claim 3 and atleast one of the following: surfactant, solid or liquid diluent.
 8. Acomposition suitable for controlling the growth of undesired vegetationwhich comprises an effective amount of a compound of claim 4 and atleast one of the following: surfactant, solid or liquid diluent.
 9. Amethod for controlling the growth of undesired vegetation whichcomprises applying to the locus to be protected an effective amount of acompound of claim
 1. 10. A method for controlling the growth ofundesired vegetation which comprises applying to the locus to beprotected an effective amount of a compound of claim
 2. 11. A method forcontrolling the growth of undesired vegetation which comprises applyingto the locus to be protected an effective amount of a compound of claim3.
 12. A method for controlling the growth of undesired vegetation whichcomprises applying to the locus to be protected an effective amount of acompound of claim 4.